Hermitian and non-Hermitian topology from photon-mediated interactions.

As light can mediate interactions between atoms in a photonic environment, engineering it for endowing the photon-mediated Hamiltonian with desired features, like robustness against disorder, is crucial in quantum research. We provide general theorems on the topology of photon-mediated interactions in terms of both Hermitian and non-Hermitian topological invariants, unveiling the phenomena of topological preservation and reversal, and revealing a system-bath topological correspondence. Depending on the Hermiticity of the environment and the parity of the spatial dimension, the atomic and photonic topological invariants turn out to be equal or opposite. Consequently, the emergence of atomic and photonic topological boundary modes with opposite group velocities in two-dimensional Hermitian topological systems is established. Owing to its general applicability, our results can guide the design of topological systems.

Stochastic Operator Variance: An Observable to Diagnose Noise and Scrambling.

Noise is ubiquitous in nature, so it is essential to characterize its effects. Considering a fluctuating Hamiltonian, we introduce an observable, the stochastic operator variance (SOV), which measures the spread of different stochastic trajectories in the space of operators. The SOV obeys an uncertainty relation and allows us to find the initial state that minimizes the spread of these trajectories. We show that the dynamics of the SOV is intimately linked to that of out-of-time-order correlators, which define the quantum Lyapunov exponent λ. Our findings are illustrated analytically and numerically in a stochastic Lipkin-Meshkov-Glick Hamiltonian undergoing energy dephasing.

Spectral Filtering Induced by Non-Hermitian Evolution with Balanced Gain and Loss: Enhancing Quantum Chaos.

The dynamical signatures of quantum chaos in an isolated system are captured by the spectral form factor, which exhibits as a function of time a dip, a ramp, and a plateau, with the ramp being governed by the correlations in the level spacing distribution. While decoherence generally suppresses these dynamical signatures, the nonlinear non-Hermitian evolution with balanced gain and loss (BGL) in an energy-dephasing scenario can enhance manifestations of quantum chaos. In the Sachdev-Ye-Kitaev model and random matrix Hamiltonians, BGL increases the span of the ramp, lowering the dip as well as the value of the plateau, providing an experimentally realizable physical mechanism for spectral filtering. The chaos enhancement due to BGL is optimal over a family of filter functions that can be engineered with fluctuating Hamiltonians.

Comparison of the Energy-Transfer Rates in Structural and Spectral Variants of the B800-850 Complex from Purple Bacteria.

Photosynthetic light harvesting can occur with a remarkable near-unity quantum efficiency. The B800-850 complex, also known as light-harvesting complex 2 (LH2), is the primary light-harvesting complex in purple bacteria and has been extensively studied as a model system. The bacteriochlorophylls of the B800-850 complex are organized into two concentric rings, known as the B800 and B850 rings. However, depending on the species and growth conditions, the number of constituent subunits, the pigment geometry, and the absorption energies vary. While the dynamics of some B800-850 variants have been exhaustively characterized, others have not been measured. Furthermore, a direct and simultaneous comparison of how both structural and spectral differences between variants affect these dynamics has not been performed. In this work, we utilize ultrafast transient absorption measurements to compare the B800 to B850 energy-transfer rates in the B800-850 complex as a function of the number of subunits, geometry, and absorption energies. The nonameric B800-850 complex from Rhodobacter (Rb.) sphaeroides is 40% faster than the octameric B800-850 complex from Rhodospirillum (Rs.) molischianum, consistent with structure-based predictions. In contrast, the blue-shifted B800-820 complex from Rs. molischianum is only 20% faster than the B800-850 complex from Rs. molischianum despite an increase in the spectral overlap between the rings that would be expected to produce a larger increase in the energy-transfer rate. These measurements support current models that contain dark, higher-lying excitonic states to bridge the energy gap between rings, thereby maintaining similar energy-transfer dynamics. Overall, these results demonstrate that energy-transfer dynamics in the B800-850 complex are robust to the spectral and structural variations between species used to optimize energy capture and flow in purple bacteria.

Extreme Decoherence and Quantum Chaos.

We study the ultimate limits to the decoherence rate associated with dephasing processes. Fluctuating chaotic quantum systems are shown to exhibit extreme decoherence, with a rate that scales exponentially with the particle number, thus exceeding the polynomial dependence of systems with fluctuating k-body interactions. Our findings suggest the use of quantum chaotic systems as a natural test bed for spontaneous wave function collapse models. We further discuss the implications on the decoherence of AdS/CFT black holes resulting from the unitarity loss associated with energy dephasing.

Superadiabatic quantum friction suppression in finite-time thermodynamics.

Optimal performance of thermal machines is reached by suppressing friction. Friction in quantum thermodynamics results from fast driving schemes that generate nonadiabatic excitations. The far-from-equilibrium dynamics of quantum devices can be tailored by shortcuts to adiabaticity to suppress quantum friction. We experimentally demonstrate friction-free superadiabatic strokes with a trapped unitary Fermi gas as a working substance and establish the equivalence between the superadiabatic work and its adiabatic value.

Impact of the lipid bilayer on energy transfer kinetics in the photosynthetic protein LH2.

Photosynthetic purple bacteria convert solar energy to chemical energy with near unity quantum efficiency. The light-harvesting process begins with absorption of solar energy by an antenna protein called Light-Harvesting Complex 2 (LH2). Energy is subsequently transferred within LH2 and then through a network of additional light-harvesting proteins to a central location, termed the reaction center, where charge separation occurs. The energy transfer dynamics of LH2 are highly sensitive to intermolecular distances and relative organizations. As a result, minor structural perturbations can cause significant changes in these dynamics. Previous experiments have primarily been performed in two ways. One uses non-native samples where LH2 is solubilized in detergent, which can alter protein structure. The other uses complex membranes that contain multiple proteins within a large lipid area, which make it difficult to identify and distinguish perturbations caused by protein-protein interactions and lipid-protein interactions. Here, we introduce the use of the biochemical platform of model membrane discs to study the energy transfer dynamics of photosynthetic light-harvesting complexes in a near-native environment. We incorporate a single LH2 from Rhodobacter sphaeroides into membrane discs that provide a spectroscopically amenable sample in an environment more physiological than detergent but less complex than traditional membranes. This provides a simplified system to understand an individual protein and how the lipid-protein interaction affects energy transfer dynamics. We compare the energy transfer rates of detergent-solubilized LH2 with those of LH2 in membrane discs using transient absorption spectroscopy and transient absorption anisotropy. For one key energy transfer step in LH2, we observe a 30% enhancement of the rate for LH2 in membrane discs compared to that in detergent. Based on experimental results and theoretical modeling, we attribute this difference to tilting of the peripheral bacteriochlorophyll in the B800 band. These results highlight the importance of well-defined systems with near-native membrane conditions for physiologically-relevant measurements.

Light Adaptation in Phycobilisome Antennas: Influence on the Rod Length and Structural Arrangement.

Phycobilisomes, the light-harvesting antennas of cyanobacteria, can adapt to a wide range of environments thanks to a composition and function response to stress conditions. We study how structural changes influence excitation transfer in these supercomplexes. Specifically, we show the influence of the rod length on the photon absorption and subsequent excitation transport to the core. Despite the fact that the efficiency of individual disks on the rod decreases with increasing rod length, we find an optimal length for which the average rod efficiency is maximal. Combining this study with experimental structural measurements, we propose models for the arrangement of the phycobiliproteins inside the thylakoid membranes, evaluate the importance of rod length, and predict the corresponding transport properties for different cyanobacterial species. This analysis, which links the functional and structural properties of full phycobilisome complexes, thus provides further rationales to help resolve their exact structure.

Construction of Multichromophoric Spectra from Monomer Data: Applications to Resonant Energy Transfer.

We develop a model that establishes a quantitative link between the physical properties of molecular aggregates and their constituent building blocks. The relation is built on the coherent potential approximation, calibrated against exact results, and proven reliable for a wide range of parameters. It provides a practical method to compute spectra and transfer rates in multichromophoric systems from experimentally accessible monomer data. Applications to Förster energy transfer reveal optimal transfer rates as functions of both the system-bath coupling and intra-aggregate coherence.

Transform-limited-pulse representation of excitation with natural incoherent light.

The excitation of molecular systems by natural incoherent light relevant, for example, to photosynthetic light-harvesting is examined. We show that the result of linear excitation with natural incoherent light can be obtained using incident light described in terms of transform limited pulses, as opposed to conventional classical representations with explicit random character. The derived expressions allow for computations to be done directly for any thermal light spectrum using a simple wave function formalism and provide a route to the experimental determination of natural incoherent excitation using pulsed laser techniques. Pulses associated with solar and cosmic microwave background radiation are provided as examples.

Thermal light cannot be represented as a statistical mixture of single pulses.

We ask whether or not thermal light can be represented as a mixture of single broadband coherent pulses. We find that it cannot. Such a mixture is simply not rich enough to mimic thermal light; indeed, it cannot even reproduce the first-order correlation function. We show that it is possible to construct a modified mixture of single coherent pulses that does yield the correct first-order correlation function at equal space points. However, as we then demonstrate, such a mixture cannot reproduce the second-order correlation function.

Coherence in energy transfer and photosynthesis.

Ultrafast energy transfer is used to transmit electronic excitation among the many molecules in photosynthetic antenna complexes. Recent experiments and theories have highlighted the role of coherent transfer in femtosecond studies of these proteins, suggesting the need for accurate dynamical models to capture the subtle characteristics of energy transfer mechanisms. Here we discuss how to think about coherence in light harvesting and electronic energy transfer. We review the various fundamental concepts of coherence, spanning from classical phenomena to the quantum superposition, and define coherence in electronic energy transfer. We describe the current status of experimental studies on light-harvesting complexes. Insights into the microscopic process are presented to highlight how and why this is a challenging problem to elucidate. We present an overview of the applicable dynamical theories to model energy transfer in the intermediate coupling regime.

Enhancement of vibronic and ground-state vibrational coherences in 2D spectra of photosynthetic complexes.

A vibronic-exciton model is applied to investigate the recently proposed mechanism of enhancement of coherent oscillations due to mixing of electronic and nuclear degrees of freedom. We study a dimer system to elucidate the role of resonance coupling, site energies, vibrational frequency and energy disorder in the enhancement of vibronic-exciton and ground-state vibrational coherences, and to identify regimes where this enhancement is significant. For a heterodimer representing two coupled bachteriochloropylls of the FMO complex, long-lived vibronic coherences are found to be generated only when the frequency of the mode is in the vicinity of the electronic energy difference. Although the vibronic-exciton coherences exhibit a larger initial amplitude compared to the ground-state vibrational coherences, we conclude that, due to the dephasing of the former, both type of coherences have a similar magnitude at longer population time.